Performance Analysis of a Natural Dye Based Dye Sensitized Solar

International Journal of Science and Research (IJSR) ISSN (Online): 2319-7064

Index Copernicus Value (2013): 6.14 | Impact Factor (2013): 4.438

Volume 4 Issue 8, August 2015

www.ijsr.net Licensed Under Creative Commons Attribution CC BY

Performance Analysis of a Natural Dye Based Dye

Sensitized Solar Cell

Md. Helal Miah1 , Zahangir Alam

2

1,2Bangladesh University of Business and Technology, Commerce College Road, Mirpur, Dhaka 1216, Bangladesh

Abstract: The dye-sensitized solar cell (DSSC) technology, taken as a new generation of photovoltaics, is an efficient and economical

way to directly convert solar energy into electricity. The significant recent development of the DSSC technology has demonstrated its

promise for future renewable solar electricity generation. In this paper a solar cell using DSSC technology has been proposed where a

common Bangladeshi seasonal fruit, blackberry (syzygium cumini) has been used as the sensitizer. TiO2 has been used as the n-type

semiconductor material and for the experimental purpose a 500 Watt halogen lamp has been used. The performance has been analyzed

by using platinum counter electrode. The experimental study has been performed in the Laboratory of University of Dhaka.

Keywords: Solar Cell, DSSC, Natural Dye, Platinum electrode, SEM, Absorption Spectrum.

1. Introduction

A solar cell (also called photovoltaic cell) is an electrical

device that converts the energy of light directly into

electricity by the photovoltaic effect. Photovoltaic is the field

of technology and research related to the practical

application of photovoltaic cells in producing electricity

from light, though it is often used specifically to refer to the

generation of electricity from sunlight.

Fossil fuels are being depleted and produces by-product like

carbon dioxide, carbon monoxide, sulphur dioxide which

contributes to global warming[1]. There is a need to find

alternative source of energy. Some alternative energy sources

such as hydroelectricity or wind are limited to areas with

windy environments or flowing rivers. On the other hand, sun

allows all parts of the world to use its energy. Solar energy is

not only environmentally safe, but also a source of energy

that will exist for billions of years. The solar cell with the

highest efficiency currently, 25%, is a silicon p- n junction

solar cell [2]. The production cost of these crystalline solar

cells is very high, and that is one of the hurdles for the mass

use of this technology. In 1991, Michael Gratzel created a

low-cost dye sensitized solar cell (DSSC) with titanium (IV)

oxide (TiO2) as a wide band-gap semiconducting oxide and a

ruthenium based dye to sensitized TiO2 and obtained a solar

cell efficiency of 10.4% [3].

The dye sensitized solar cell (DSSC) technology has been

developed for low-cost, high-efficiency solar-to-electricity

conversion. A DSSC with an effective area of 1.004 cm2

under global AM1.5 spectrum (1000 Wm-2

) at 25 C exhibits

a short-circuit current of 21.8 mAcm-2

and an open-circuit

voltage of 0.729 V with a fill factor of 0.652 and an

efficiency of 10.4 ± 0.3 % [4]. The submodule mode of

DSSC with an effective area of 26.48 cm2 has achieved an

efficiency of 7.9 ± 0.3 %. In fact, the theoretical efficiency

for the terrestrial cell can reach as high as 30 % [5]

indicating that there is much room for enhancing the energy

conversion efficiency of DSSC. Despite the fact that the

prices of conventional fuels are rising, the DSSC has been

following the trend of declining costs and eventually it will

constitute 20% or greater proportion in the growing solar-to-

electricity market [6].

In this paper we have constructed a DSSC for the first time in

our university. As the wide band gap semiconducting oxide

we have used nano particle TiO2. TiO2 is widely available and

is common in everyday household items, such as sunscreen.

To sensitize the oxide we have used a natural dye extracted

from blackberry (syzygium cumini), a seasonal fruit in

Bangladesh. As the counter electrode we have used platinum.

We also have used an iodide/tri-iodide couple electrolyte

solution in the solar cell as a charge carrier.

In laboratory we have used a halogen bulb as the light source

to get the Current-Voltage characteristic of the cell. Power-

Voltage characteristic was also obtained. This was

understandable since dye from black berry absorbs light in

the UV region while our light source didn’t have any light in

that region.

2. Theoretical Background

When the light from the sun falls on any solar cell, three

basic operations consists of absorption, separation and

collection are held [7] .For DSSC, it applied absorption

process to absorb the photon from the sun rays. The DSSC

are fabricated by sandwiching a dye anchored mesoporous

metal oxide, known as photoelectrode, between two

conducting glass plates (such as fluorine-doped indium tin

oxide (FTO)) in the presence of an electrolyte [8] Basically,

there are four main components in DSSC such as light

source, semiconductor, sensitizer and the electrolyte [9]

which play important role in the DSSC. Each of the

components has their own function.

The DSSC principle is applied from the photosynthesis

process and diffusion is a major mechanism for electron to

travel through the oxide layer [10]. The electronic process in

DSSC involved several steps as shown in Figure 1 & 2.

Paper ID: SUB157505 1112

http://en.wikipedia.org/wiki/Light

http://en.wikipedia.org/wiki/Electricity

http://en.wikipedia.org/wiki/Photovoltaic_effect

http://en.wikipedia.org/wiki/Photovoltaics





Figure1: Schematic of a liquid electrolyte DSSC with

external circuit [11]

Figure2: Schematic illustration of electron movement of dye

sensitized solar cell [12].

The steps involve:

(a) When the photon from the sunrays enters into the DSSC

device. According to Eq. (1), the sensitizer, S absorbs a

photon of wavelength, hν corresponding to the energy

difference between its highest occupied molecular orbital

(HOMO) and lowest unoccupied molecular orbital (LUMO)

which leads to excited sensitizer state, S* known as photo

excitation.

(b) Photo excitation, S* of this sensitizer is then injected the

electron,e refer to Eq. (2), which travel through the

nanostructured film by diffusion into the conduction band of

the semiconductor (mesoporous),usually using TiO2 (high

band gap: 3.2 eV) to reach TCO on glass substrate as a

current collector. Meanwhile according to [13], the hole

generated by photon excitation remains on the molecule

during this process, since the HOMO of dye is separated

from all other energy levels of the device. There is no energy

channel for the hole to diffuse into TiO2photoanode. As a

result, the hole is eventually filled up by electrons from

electrolyte ions, which conduct current between the cathode

and the dye molecule.

(c) The injected electron,e flows through the semiconductor

network to arrive at the back contact by through the external

load.

(d) By referring Eq. (3), the injected electron,e at back

contact react in reduction of oxidized dye by iodide produces

triiodide, I-3

to reduce the redox mediator. At the same time,

the triiodide, I-3

diffuses to counter electrode and accepts

electrons from external load, regenerating the iodides [14].

(e) Then, iodide wills donates electron to the oxidized

sensitizer, S+ that obtained at anode from Eq. (2) and

regenerates the sensitizer which in turn regenerates the

sensitizer as shown in Eq. (4). This process occurs quickly

and results in no net chemical change [15]

(f) However, Eqs. (5) and (6) are undesirable reactions either

with oxidized sensitizer or with the oxidized redox couple at

the TiO2 surface. Consequently, performance of the cell will

be affect.

This process goes in cycle and consequently current flows

through the external circuit as long as light are incident on

the cell [16]. The equations below show the reaction of the

sensitizer and electron in the DSSC [17-20] that have been

explained.

S (absorbed) + hν→ S*(absorbed) (1)

S*(absorbed) → S+

(absorbed) + e-(injected) (2)

𝐈𝟑− + 2 e

-(cathode) → 3I

-(cathode) (3)

S+

(absorbed) +𝟑

𝟐 I

- → S (absorbed) +

𝟏

𝟐𝐈𝟑− (4)

S+

(absorbed) + e-(TiO2) → S (absorbed) (5)

𝐈𝟑− + 2 e

-(TiO2) → 3I

-(Anode) (6)

By referring the above figure, it shows the illustration of

electron movement in the first step until to last step. This

process will go on continuously as long as the sun rays

incident on the cell. According to Fig. 2, the maximum

voltage in DSSC is determined by the energy separation

between Fermi level and the electrolyte chemical potential

(Eredox). The photocurrent level is dependent on the

separation level of HOMO-LUMO as example, if the energy

separation of LUMO is increase, it will improve the electron

injection into the conduction band of TiO2 effectively [21].

Besides, if the HOMO level accept the donated electrons

from redox mediator effectively, it show that the energy

different between the HOMO and redox mediator is positive.

We can conclude that photo voltage is generally determined

by the energy difference between the Fermi level of TiO2

and redox potential of electrolyte. The anode-cathode

potential difference, namely, the open-circuit voltage Voc, is

mainly determined by the difference between conduction

band bottom and electrolyte anion energy level [22]. At

short-circuit condition, the Fermi energy level decreases

in the direction of the back contact (charge collector)

due to difference in electron concentration with TiO2 film

distance. On the other hand, at open- circuit condition the

Fermi energy level is constant across the entire film [23].

One of the most important problems is the recombination of

the photo injected electrons in the conduction band of the

semiconductor with the oxidized dyes and the triiodide in the

electrolyte. In DSSC, the individual particle size is so small

that the formation of a space charge region is impossible [24-

25]. This indicates that the recombination rate of the photo

injected electrons is very high due to the absence of an

energy barrier at the electrode/electrolyte interface [25]. So

many studies to reduce the recombination at the interface

were tried such as fabrication of bilayer electrode,






preparation of composite semiconductor electrode, and

passivation of semiconductor electrode using electro

polymerization method and so on [25]

3. Experimental Details

For the experimental study, several DSSC sample was made

the following procedure was followed for that.

3.1 FTO Coated Glass

We used Fluorine doped tin oxide [FTO] coated Glass as a

substrate in our experiment. FTO coated glass is generally of

float (soda-lime) glass using polished and unpolished

substrates. These products are for use in spectro-

electrochemistry, liquid crystal display [LCD] research and

development, organic light emitting diode [OLED] research

and development, phosphor research and quality control,

electro- luminescent display [ELD] development,

photovoltaic development, and other applications that require

the properties of FTO coated glass such as:

Electrically conductive and optically transparent.

High VIS-NIR light transmission.

High quality glass substrate.

SiO2 barrier layer.

Low roughness.

Low sheet resistance ~14ohm/sq.

Uniform transmission up to ~90%.

Reflecting in the infrared range.

3.2 Platinum coating

FTO coated glass plates were cleaned using following

procedure:

Washed with detergent water in ultrasonic bath for 10

minutes.

Then cleaned in distilled water for 10 minutes.

Cleaned with acetone for 10 minutes in ultrasonic bath.

Finally Cleaned with isopropyle alchohol for 10 minutes

in ultrasonic bath.

We have placed FTO glass plate into the sputter coater. Then

we have made a thin platinum layer on conducting side of

FTO glass plate.

3.3 Preparation of TiO2 coated slide:

At first TiO2 paste was made adopting the following

procedure: 9 ml vinegar is added to 6 g titanium dioxide and

mixed until it became smooth. Then one drop of dishwashing

detergent is added to the suspension and kept in that

condition for 15 minutes.

We took one piece of FTO glass plate which has been

cleaned thoroughly as described before and have put 0.04mm

thickness scotch tape on two sides of the conducting side of

FTO glass. Then we used a small paintbrush to distribute a

thin layer of the TiO2 solution across the conducting surface

of a FTO glass shown in Figure 3.

Figure 3: TiO2 substrate

So the thickness of the TiO2 layer is 0.04mm. We allowed

the slide to dry for a few minutes, placed the TiO2 coated

slide on a hotplate at 300C for around 20 minutes. Then we

turned off the heater so that slide can come back the room

temperature slowly.

3.4 Preparation of Dye Solution

We took four dry black berries and collected their barks and

made a paste with them, then immersed the paste in 2 ml

ethanol kept it there for overnight so that dye can be

absorbed in ethanol effectively. Next morning we have put

the solution in ultrasonic bath for 30 minutes. Finally we

filtered to solution to collect dye.

3.5 Sensitizing with dye

For that we put a drop of dye on top of the previously

prepared TiO2 coated substrates. For the blackberry dyes we

had to keep the dye on top of TiO2 coated surface for several

hours for the dye to properly stain the TiO2 matrix. After

staining we rinsed the slides with distilled water and allowed

them to dry for a few minutes.

Figure 4: Dye sensitized TiO2 substrate

3.6 Preparation of Iodide Electrolyte Solution

We have dissolved 0.127 g Iodine in 10 ml of ethylene

glycol. Next added 0.83 g Potassium Iodide (KI), then

stirred and stored in a dark container.






3.7 Assembly of the Solar Cell

Figure 5: Assembly of the Solar Cell

We have put 0.181mm thickness scotch tape (acts as spacer)

on two sides of dye sensitized TiO2 coated side. We then

placed the platinum coated slide face down on top of the

TiO2 coated slide. So cell thickness is 0.181 mm. We used

two binder clips to hold the two slides together as shown in

fig.-5. Then with a dropper, added one to two drops of liquid

iodide/iodine electrolyte solution to the space between the

two slides. The solution was drawn into the cell by capillary

action .Attached the alligator clips to the two overhanging

edges of the slides and attached the clip l to multi-meter with

the negative terminal attached to the TiO2 coated slide, and

the positive terminal attached to the platinum coated slide

3.8 Photocurrent Measurement:

(a)

(b)

Figure 6: (a) Circuit diagram, (b) Measurement of I-V

characteristics

Solar cell is connected as shown in figure 6 using cables.

Light from a 500 watt halogen bulb is used as a light

source and the sample cells were always 70 cm away from

the light source for all the I-V measurements for all the

cells discussed in this thesis.

At first the load resistance was fixed at the maximum

value and the corresponding voltage was recorded later the

resistance was decreased gradually and the corresponding

voltages was recorded.

The photocurrent was calculated for each recorded data

using Ohm’s law.

I = V / R

Also the power for each load resistance was calculated

using the following formula.

P = V x I

4. Results and discussion

4.1 SEM Image of TiO2 coated glass slide

We have used 100nm TiO2 to make the paste, but from the

image we see that nano particles were clustered together with

an average size around 200nm-300nm. From the image we

can also observe that there are lots of pores in TiO2 matrix.

Figure 7: Image of TiO2

This is very important so that dye can enter the matrix and

properly stain the maximum area possible of the TiO2 matrix.

4.2 Energy dispersive spectroscopy (EDS)

Figure 8: Graph of elemental analysis of TiO2 thin film

From the EDS report we see that TiO2 thin filmcontains

68.8% oxygen (O) and 31.42% titanium (Ti) as expected.

4.3 I-V and P-V data

4.3.1 Study of blackberry dye as sensitizer

As mentioned before we have used blackberry dye for

sensitizing TiO2. Data for I-V and P-V measurement are

plotted below.

TiO2






0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

0.0

1.0x10-6

2.0x10-6

3.0x10-6

4.0x10-6

5.0x10-6

6.0x10-6

7.0x10-6

Cu

rren

t(A

/cm

2)

Voltage(Volt)

Dye-Black berry,A seasonal fruits of Bangladesh

Platinum Electrode

Figure 9: Cell Voltage (volt) Vs Cell current (A/cm

2)

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

0.0

1.0x10-7

2.0x10-7

3.0x10-7

4.0x10-7

5.0x10-7

6.0x10-7

7.0x10-7

8.0x10-7

Po

wer(

W/c

m2)

Voltage(Volt)

Dye- Black berry, A seasonal fruits of Bangladesh

Platinum Electrode

Figure 10: Cell Voltage (Volt) Vs Power (W/cm

2)

The maximum power along with the short circuit current and

open circuit voltage of the cell are given below:

Table 1: Data for Short circuit current, Open Circuit

Voltage, Maximum Power and Fill factor Short circuit

current (ISC)

(A/cm2)

Open Circuit

Voltage (VOC)

(Volt)

Maximum

Power (Pmax)

(W/cm2)

Fill factor

6.96x10-6 0.318 7.14x10-7 32.26%

To explain the result we need to study the light spectrum of

halogen bulb in comparison to solar light and also we need to

know the absorption spectrum of the dyes used. These are

discussed below.

4.3.2 Halogen spectrum

As mentioned before since we didn’t have a solar simulator

we used a 500 watt halogen bulb as the light source. The

spectrum of halogen light is shown in the figure 11 and it

showed that halogen light gives ray from 500nm to 1000nm

with a maximum intensity at around 750nm. This showed

that unlike sun there is no UV light emitted by this source.

Figure 11: Halogen spectrum [26]

For comparison purpose we have also added the sun’s

spectrum from literature [27] in the next figure12.

Figure 12: solar spectrum [27]

It is clear that absence of UV light from around 200 nm to

around 400 nm in the halogen bulb is responsible for smaller

power generated in our DSSCs in comparison to the power

obtained by the others [28].

4.3.3 Absorption spectrum of dyes

We have taken the absorption spectrum of Syzygium cumini

(Blackberry) using a UV-Vis spectrophotometer (Model no

Shimadzu: UV-1800). The data is presented in figure-13.

Also the wavelength corresponding to the maximum

efficiency and the range of wavelength where appreciable

absorption happens is tabulated in the Table 2.

200 300 400 500 600

0.0

0.5

1.0

Ab

so

rban

ce(A

.U.)

Wavelength(nm)

Figure 13: Graph of absorbance measurement

Table 2: Range of absorbance and peak position for

Syzygium cumini(Blackberry) Peak position (λmax) in nm Range of absorbance (nm)

282 200 – 400

Analyzing the above data tells us that cell sensitized with dye

extracted from black berry absorbs light from 200 to 400 nm.

Although the halogen bulb that we have used does not

produce any light in the 200 to 400 nm range as evident from

the discussion from the earlier section from dye extracted

from black berry there is appreciable absorbance from 200 to

350 nm and after that the absorbance decreases and becomes

negligible up to 580nm.






Since halogen bulb doesn’t produce any light in the UV

region and dye extracted from black berry doesn’t absorbs

much light in the visible region so the energy conversion

efficiency for this cell was very low. If we could do the

experiment using full solar spectrum simulator then the

power obtained from the cells would have been more.

Besides the use of 100nm TiO2 powder contributed towards

the lower performance of the cells since using even smaller

particles more surface area can be exposed to solar light and

thus there will be a considerable increase of the possibility of

more solar light harvesting.

5. Conclusion

In this work we have constructed a DSSC for the first time in

our university. We have used Platinum as electrode in this

work. We have recorded the I-V and P-V characteristic curve

for the cell.

We have used dye extracted from black berry (Syzygium

cumini) for sensitizing TiO2 and made cell with Platinum

electrode. Data for I-V and P-V measurement showed that

the power generated is much lower than that of conventional

cells. To find an explanation of the above behavior we took

absorption spectra of the dye extracted from black berry used

in our study, the spectra showed that even the halogen bulb

that we have used does not produce any light in the 200 to

400 nm range, dye extracted from black berry has an

appreciable absorbance from 200 to 350 nm. That is the main

reason for lower power produced by the cell using dye

extracted from black berry. If we could do the experiment

using full solar spectrum simulator then the power obtained

from the cells would have been more. Besides the use of

100nm TiO2 powder contributed towards the lower

performance of the cells since using even smaller sized

particles, more surface area can be exposed to light and

better output power can be achieved.

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Author Profile

Md. Helal Miah graduated with B. Sc. & M.S. degree

in Physics from the University of Dhaka, Bangladesh

in 2008, 2009 respectively. He is a lecturer in physics,

department of EEE at Bangladesh university of

Business and technology (BUBT). The field of research is dye

sensitized solar cells.

Zahangir Alam is currently working as a lecturer in

physics of the Department of Electrical & Electronic

Engineering at Bangladesh University of Business

&Technology (BUBT). He received B.Sc. & M.S.

degrees in Physics from the University of Dhaka, Bangladesh. His

field of research interest is health physics, medical physics and solar

cell.


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Performance Analysis of a Natural Dye Based Dye Sensitized Solar